Fluid-storing material



Patented Mar. 19, 1929.

UNITED STATES PATENT OFFICE. FBEEBICK G. REYES, OF CAMBRIDGE, MASSACHUSETTS, A SSIGNOB, BY MTJSNE sremrrmrs, 'ro NATIONAL .REFRIGERATING COMPANY, or Bos'ron; massncnoslurs, A conronnrron or mssncrrusn'rrs. I

FLUID-STORING MATERIAL.

Ho Drawing. Original application filed liovembere, 1923, Serial No. 673,103. Divided and this application filed January 15, 1925. Serial No. 2,601.

Serial Number 475,855 of which this application is. a continuation-in part. This application furthermore is a'continuation in. part of my application filed Sept. 26, 1922, Serial No. 590,668. This application is a division of my application Serial No. 673,103, filed November 6, 1923. By way of example, the liquid 01' gas to be stored is referred to hereinafter as a refrigerant, such as ammonia, which is commonly used in refrigerating apparatus, although it is to be understood that my invention is not limited to the use of this particular fluid or to refrigerating apparatus.

The storing material in a still or generator is an important element in a refrigerator apparatus and should preferably be a solid material capable of taking up the refrigerant and holding it in such a physical state as to maintain its vapor pressure below that of the free liquid. Several important factors enter into the production of a practical and highly efficient storing material to be used in a safe refrigerator apparatus, and the desirable properties or rgualities of such a materlal are:

1. It must e stable at elevated temperatures; r

2. It must not react under any conditions of use with the metal used to contain it,

3. The unit weight of the material must take a large amount of refrigerant;

4. Its heat capacity must be as small as possible and,

40 5. It must be brought into such a physical state by the addition of cementitious and other substances of a reaction velocity promoting character and preferred physical and chemical treatment as to remain under use in the form of discrete hard and porous granules capable of presenting a large surface for ready speedy absorption of the refrigerant, this being a prime requlsite for rapid and eificient refrigeration.

It is evident in selecting a cementitious substance designed to confer the property of hardness in the grains of the final storing material that the chosen cements or cement- 1ng compounds retain their property at high temperatures, to which on occasion the gas storing material may be exposed.

I have found that by special treatment of cellular material, such as charcoal, with certain metallic salts, for example, zinc chloride,

chromic acid, etc., a substance is produced which I term activated charcoal and one well suited as a storing material for use in refrigerating apparatus. This material condenses the refrigerant on its surfaces, holding it with great tenacity at room temperature, and readily and completely giving it up at moderately elevated temperatures, 150 C.

The use of-"activa-ted charcoal as astoring material in refrigerating machine's, due to its large bulk per unit weight necessitates a large still which in turn offers a large surface for radiation involving a possible diminution in the efiiciency of operation of the apparatus, as compared with the efliciencies obtainable when other ,materials are used. Moreover because of the small specific quantity'of refrigerant taken up much energy is lost in heating the charcoal. The great advantage, however, of an absorbent such as charcoal is that it takes up the refrigerant with extreme rapidity and this is an advantage at the end of the distillation period when .it is necessary to start the return of the re frigerant promptly from the refrigerating chamber. For example, one gram of charcoal in its optimum state of activity has a heat capacity of about .25 calories per gram. The maximum amount of ammonia, for ex ample, which a certain'sample will take up is, for example, 0125 gram and the heat necessary to drive this off at 150 C. is about 59 calories. In heating to 150 0, therefore, about'31 calories are used up owing'tothe heat capacity ofthe absorbent material "so that 34 percent of the energy has been thrown away on heating the material. It is clear therefore that an increase in efliciency would be obtained if less heat were necessary to disengage the gas from the storing material and less heat were necessary to raise thematerial to the point where the refrigerant is given up. In the case of other absorbing substances ticularly the highly deliquescent ones being.

active andreadily available for the purpose of absorbing and storing fluids and gases, and of these substances calcium chloride, because of its cheapness and availability in the market, has been selected for the purposes of illustrating my invention, as hereinafter set forth. Eachgram of the last named substance takes up 1.22 grams of ammonia and the ammonia moreover enters into chemical combinations as stated in the formula:

There are other calcium chloride compounds, .one sand to contain 4 molecules of ammonia, I

but the formula given corresponds to the. maximum amount of ammonia and moreover possesses a very small pressure of ammonia at ordinary temperature. It was found in using this material alone that the rate at which it would take up ammonia was very small due to a tendency to pulverize and to pack, thus preventing ready access of the refrigerant.

It became, therefore. a problem of discovering the best physical state and mode of preparation of this material so as to maintain it in the still under the conditions of operation in such astate that it would expose the -maximum surface, retain a high relative velocity and remain in a hard, durable yet porous condition offering no resist ance to the free circulation of the refrigerant among the granulesof the absorbent. It was found that Portland cementmix'ed with the chloride to the amount of 10 to'15 per cent and suflicient water to form a thick paste could-be slowly baked in the presence of ammonia so as to give a. material in hard porous grains'which maintained their form under repeated heating and cooling in the distillingvand t-akingup of the ammonia. This material, however, while serviceable may develop a tendency, due to its composition, to dehydrate, when operated at extremely elevated temperatures.

It has been known for a long time that halides of the metals form with oxides of the metals certain oxy-halides which are in efiecthard cements. For example, zinc chloride forms with zinc oxide certain oxy-chlorides and also that magnesium-chloride formswith magnesium oxide similar oxy-chlorides which are, as stated above, in effect hard cements. Moreover, it is a fact of common observation that sodium silicate will, upon heating, blow up to a porous, spongy mass. I make use of the above mentioned characteristics of these substances together with such heating and cooling and changes of volume produced by taking upand disengaging re-,

frigerant, as follows:

Dry calcium chloride is mixed with 10 per cent of molecular proportions d'ry zinc oxide (ZnO) and zinc chloride (ZnCl or is mixed with -10 per cent of molecular proportions of dry magnesium oxide (MgO) and magnesium chloride (MgCl After thorough incorporation in a ball mill the selected mixture is then moistened with sodium silicate or other alkali-metal silicate such as potassium or even beryllium silicate in the mixture when dry and the pasty mass dried first in a current of air at about 250 C. The materialis then broken up and sifted and then treated at 500 C. in the presence of ammonia, whereupon an extremely porous, hard material is obtained which possesses the quality of taking up ammonia with great rapidity, and, moreover, one which does not decompose on heating to a high temperature GOO-750 C.).

When either one of the calcium chloride mixtures is used alone as the storing material, due to the fact that it is of small bulk and possesses the propert of rapidly taking up a large amount of re igerant per unit weight when cooled and readily giving it up when heated to a temperature of about 150 C a smaller containing still is used in the apparatus than when activated charcoal alone is used as the storing material therein,

I have found, also, by mixing approximately equal volumes of activated charcoal and one or the other of the above mentioned calcium chloride mixtures in a small still, the charcoal serving to support and to maintain even distribution of the chloride mixture throughout the still and aiding to promptly start the refrigerating period due to the extreme speed with which it takes up the refrigerant, that highly efiicient operation of the apparatus is obtained.

Furthermore, I have discovered that by adding alundum cement, a product obtain- I able in the market under that name, which is a flour like powder, and appears to be essentially aluminum oxide with additions of mathe addition of a quantity, up to 10 percent,

of alundum cement in the preparation of either the zinc oxy-chloride mixture or the magnesium oxychloride mixture,'mentioned above, to increase the speed of absorption of said mixture, and by varying the quantity added to any given mixture the-speed of absorption of the mixture can-be increased or decreased, as desired.

It is sometimes found desirable to include in any of the mixtures mentioned above, or to add thereto, other absorbing, adsorbing, or storing materials, such as ferric chloride, chromic chloride, copper sulphate, and the like, or kieselguhr, ground porcelain, pumice and the like, or iron oxide, or aluminum oxide and the like, to alter either the absorbing characteristic or the hardness of the mixture,

takethe orto meet varying conditions of service of the storing'material.

The ferric chloride, chromic chloride, andlike substances when included would serve as contact or transfer mediums in the absorbing action'of the saidabove mentioned mixtures on the refrigerant. For certain purposes and for desired effects the ferric chloride, chromium chloride, and the like could be used to materially or completely place of the said above mentioned mixtures.

What I claim is:

1. A hard storing material'for fluids, comprising calcium chloride, and magnesium oxy-chloride, and alundum cement.

- 2. A hard storing material for fluids, comprising anhydrous calcium chloride, and magnesium oxy-chloride, and alundum cement.

a halide capable of forming addition compounds with fluids, an oxy-chloride cement, and alundum cement.

4. A storing material for fluids comprising a metal halide-capable of forming addition compounds'with fluids, an 'oxy-chloride cement, and alundum cement.

In testimony whereof I hereto aflix my signature.

' FREDERICK G. 'KEYES.

3. A storing material for fluids comprising I 

